CN106831878B - A kind of siliceous and fluorine DOPO derivative flame retardant and preparation method thereof - Google Patents
A kind of siliceous and fluorine DOPO derivative flame retardant and preparation method thereof Download PDFInfo
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- CN106831878B CN106831878B CN201710119891.6A CN201710119891A CN106831878B CN 106831878 B CN106831878 B CN 106831878B CN 201710119891 A CN201710119891 A CN 201710119891A CN 106831878 B CN106831878 B CN 106831878B
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 54
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 49
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical class C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 36
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011737 fluorine Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- GAPOASFZXBWUGS-UHFFFAOYSA-N 2,2,2-trifluoro-1-(3-trimethylsilylphenyl)ethanone Chemical compound C[Si](C)(C)C1=CC=CC(C(=O)C(F)(F)F)=C1 GAPOASFZXBWUGS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229950004402 zifrosilone Drugs 0.000 claims abstract description 12
- 239000013067 intermediate product Substances 0.000 claims abstract description 11
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- -1 after reaction Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000001035 drying Methods 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000012757 flame retardant agent Substances 0.000 abstract description 3
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- BSYJHYLAMMJNRC-UHFFFAOYSA-N 2,4,4-trimethylpentan-2-ol Chemical compound CC(C)(C)CC(C)(C)O BSYJHYLAMMJNRC-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention relates to technical field of flame retardant, and in particular to a kind of siliceous and fluorine DOPO derivative flame retardant, structural formula are as follows:The preparation method of a kind of siliceous and fluorine DOPO derivative flame retardant, includes the following steps: that (1) heats tricresyl phosphate (4- aminophenyl) ester and Zifrosilone in a solvent, after reaction, obtains the reaction system containing intermediate product I；(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction, washing, drying obtain siliceous and fluorine DOPO derivative flame retardant.A kind of siliceous and fluorine DOPO derivative flame retardant and preparation method thereof, with the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases；When flame retardant agent content reaches 5-10%, solidfied material can achieve UL-94, and V-0 grades.
Description
Technical field
The present invention relates to technical field of flame retardant, and in particular to a kind of siliceous and fluorine DOPO derivative flame retardant and its system
Preparation Method.
Background technique
Halogenated flame retardant is containing halogens and with a based flame retardant of halogens fire retardation.Four kinds of halogen system
Halogen system element fluorine (F), chlorine (Cl), bromine (Br), iodine (I) all have anti-flammability, and flame retardant effect is successively increased by the sequence of F, Cl, Br, I
By force.It is most strong with iodine flame retardant.In production, only chlorine class and brominated flame retardant are widely used and fluorine class and iodine based flame retardant
Rare application, this is because C-F key is too strong and cannot effectively capture the C-I key of free radical and the fire retardant containing I in fluorine-containing fire retardant
Too weak easily being destroyed affects polymer performance (such as photostability), has lost flame retardant property just below degradation temperature.
9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, abbreviation DOPO contain P-H key in structure, to alkene
Hydrocarbon, epoxide and the great activity of carbonyls can react and generate many derivatives.DOPO and its derivative are due to molecule
Contain cyclohexyl biphenyl, phenanthrene ring, O=P-O key in structure, so there is stronger flame retardant property than common organophosphorus ester.By
Saito reported its synthetic route in 1972 for the first time.DOPO and its derivative can be used as response type and additive flame retardant, close
At fire retardant Halogen, smokeless, nontoxic, do not migrate, flame retardant property is lasting.While improving the flame retardant property of material, not shadow
Ring the mechanical performances such as the mechanical strength of material.It can be used for the multiple materials such as polyamide, linear polyester, polyurethane, epoxy resin
Flame retardant treatment, foreign countries are widely used in the fire-retardant of materials such as pressurized layer, circuit board in plastics for electronics, brass.Although having
Good flame retardant property, but with the increase of additional amount, some detrimental effects can be brought to the performance of material itself.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of siliceous and fluorine DOPO derivative flame retardant
And preparation method thereof, with the increase of phosphorus content in solidfied material, the anti-flammability of solidfied material increases；When flame retardant agent content reaches 5-
When 10%, solidfied material can achieve UL94, and V-0 grades.
To achieve the purpose of the present invention, the present invention adopts the following technical scheme:
A kind of siliceous and fluorine DOPO derivative flame retardant, structural formula are as follows:
The preparation method of a kind of siliceous and fluorine DOPO derivative flame retardant, includes the following steps:
(1) tricresyl phosphate (4- aminophenyl) ester and Zifrosilone are heated in a solvent, after reaction, is obtained containing centre
The reaction system of product I；
(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction,
Washing, drying, obtain siliceous and fluorine DOPO derivative flame retardant.
Its reaction process are as follows:
Specifically, the molar ratio of tricresyl phosphate (4- aminophenyl) ester and Zifrosilone is 1:3 in above-mentioned steps (1).
Specifically, the reaction time is 5-10h in above-mentioned steps (1).
Specifically, heating temperature is 75 DEG C in above-mentioned steps (1).
Specifically, solvent is ethyl alcohol, DMF or DMSO in above-mentioned steps (1).
Specifically, the additional amount of solvent is tricresyl phosphate (4- aminophenyl) ester and Zifrosilone quality in above-mentioned steps (1)
5-9 times of sum.
Specifically, the molar ratio of the DOPO in above-mentioned steps (2) and the Zifrosilone in step (1) is 1:1.
Specifically, the reaction temperature in above-mentioned steps (2) is 75 DEG C.
Specifically, the reaction time in above-mentioned steps (2) is 5-9h.
The invention has the benefit that
(1) the siliceous DOPO derivative flame retardant with fluorine of one kind of the invention, with the increase of phosphorus content in solidfied material, Gu
The anti-flammability of compound increases；When flame retardant agent content reaches 5-10% (phosphorus content 0.36wt%-0.73wt%), solidfied material can
To reach UL-94, V-0 grades.
(2) the siliceous DOPO derivative flame retardant with fluorine of one kind of the invention has preferable due to the lower surface energy of fluorine
Surface migration so that fire retardant in use it is easy to migrate to material surface be enriched with, amount seldom under conditions of just have
There is high flame retardant and low cigarette, low toxicity evil, non-corrosive gas generate.
(3) the siliceous DOPO derivative flame retardant with fluorine of one kind of the invention, although introducing fluorine element on fire retardant,
But free radical cannot be effectively captured since C-F key is too strong, make fire retardant that there is excellent thermal stability；Contain silicon in structure
Element, with preferable flame retardant effect, smokeless, high temperature resistant, chemical stability are good, while the mechanical property of material can be improved.
Detailed description of the invention
Present invention will be further explained below with reference to the attached drawings and examples.
Fig. 1 is the DOPO derivative flame retardant nuclear magnetic spectrogram of the siliceous and fluorine of the specific embodiment of the invention 1.
Specific embodiment
Presently in connection with embodiment, the present invention is described in further detail.
Embodiment 1
A kind of synthesis step of the organic silicon fibre retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) by the Zifrosilone of the tricresyl phosphate of 11.1g (4- aminophenyl) ester and 22.2g in 75 DEG C of 166.3g ethyl alcohol
Heating 5h obtains the reaction system containing intermediate product I after reaction；
(2) DOPO of 19.5g is added in the reaction system containing intermediate product I that step (1) obtains in 75 DEG C of items
5h is heated under part, and after reaction, washing, drying obtain siliceous and fluorine DOPO derivative flame retardant, yield 86.4%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3410cm-1, C-H stretching vibration peak 3070cm-1, C-N characteristic peak 1288cm-1, C-F characteristic peak 1105cm-1, C-Si characteristic peak 1255cm-1, P-O-C characteristic peak 1032cm-1, P-O-Ph characteristic peak 1231cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1212cm-1, the out-of-plane bending vibration peak 900cm of fragrant hydrogen-1。
Nuclear magnetic spectrogram as shown in Figure 1, nuclear-magnetism test result is as follows:
1H-NMR (400MHz, DMSO-d6) δ 7.51 (m, 3H), 7.34 (l, 3H) 7.3-7.31 (k, 9H), 7.19 (j,
3H), 7.10 (i, 3H), 7.04-7.05 (g, 9H), 6.88 (f, 3H), 6.79 (e, 3H), 6.51 (d, 6H), 6.26 (c, 6H),
4.01 (b, 3H), 0.66 (a, 27H).
Embodiment 2
A kind of synthesis step of the organic silicon fibre retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) Zifrosilone of the tricresyl phosphate of 18.6g (4- aminophenyl) ester and 37g are added in 75 DEG C of 388.8g DMF
Hot 7h obtains the reaction system containing intermediate product I after reaction；
(2) DOPO of 32.4g is added in the reaction system containing intermediate product I that step (1) obtains in 75 DEG C of items
7h is heated under part, and after reaction, washing, drying obtain siliceous and fluorine DOPO derivative flame retardant, yield 86.2%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3410cm-1, C-H stretching vibration peak 3075cm-1, C-N characteristic peak 1287cm-1, C-F characteristic peak 1105cm-1, C-Si characteristic peak 1255cm-1, P-O-C characteristic peak 1033cm-1, P-O-Ph characteristic peak 1232cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1212cm-1, the out-of-plane bending vibration peak 850cm of fragrant hydrogen-1。
Embodiment 3
A kind of synthesis step of the organic silicon fibre retardant of Nitrogen-and Phosphorus-containing are as follows:
(1) by the Zifrosilone of the tricresyl phosphate of 37.1g (4- aminophenyl) ester and 73.9g in 75 DEG C of 999g DMSO
Heating 10h obtains the reaction system containing intermediate product I after reaction；
(2) DOPO of 64.9g is added in the reaction system containing intermediate product I that step (1) obtains in 75 DEG C of items
9h is heated under part, and after reaction, washing, drying obtain siliceous and fluorine DOPO derivative flame retardant, yield 86.6%.
Its infrared test result is as follows:
FTIR (KBr): N-H stretching vibration peak 3415cm-1, C-H stretching vibration peak 3085cm-1, C-N characteristic peak 1287cm-1, C-F characteristic peak 1105cm-1, C-Si characteristic peak 1254cm-1, P-O-C characteristic peak 1033cm-1, P-O-Ph characteristic peak 1232cm-1, P-Ph characteristic peak 1595cm-1, P=O characteristic peak 1212cm-1, the out-of-plane bending vibration peak 900cm of fragrant hydrogen-1。
Application Example:
Material is weighed according to table 1:
Table 1:
| Application Example | Siliceous and fluorine DOPO derivative flame retardant (g) | Polystyrene (g) | P content |
| Application Example 1 | 30 | 970 | 0.22wt% |
| Application Example 2 | 40 | 960 | 0.29wt% |
| Application Example 3 | 50 | 950 | 0.36wt% |
| Application Example 4 | 80 | 920 | 0.58wt% |
| Application Example 5 | 100 | 900 | 0.73wt% |
Siliceous and fluorine DOPO derivative flame retardant and polystyrene are uniformly mixed；It adds twin-screw extrude,
Under conditions of 200-220 DEG C of unit temperature, 210 DEG C of die head temperature, screw speed 200rpm, extruding pelletization, then through drying, it is cold
But, fire retardant polystyrene sample is obtained.UL94 testing vertical flammability is carried out to the sample, as a result shown in table 2:
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (10)
1. a kind of siliceous and fluorine DOPO derivative flame retardant, which is characterized in that its structural formula is as follows:
。
2. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as described in claim 1, it is characterised in that packet
Include following steps:
(1) tricresyl phosphate (4- aminophenyl) ester and Zifrosilone are heated in a solvent, after reaction, intermediate product must be contained
The reaction system of I；
(2) DOPO is added in the reaction system containing intermediate product I that step (1) obtains and is heated, after reaction, washed
It washs, dry, obtain siliceous and fluorine DOPO derivative flame retardant.
3. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
Stating the molar ratio of tricresyl phosphate (4- aminophenyl) ester and Zifrosilone in step (1) is 1:3.
4. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
Stating the reaction time in step (1) is 5-10h.
5. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
Stating heating temperature in step (1) is 75 DEG C.
6. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
Stating solvent in step (1) is ethyl alcohol, DMF or DMSO.
7. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
The additional amount for stating solvent in step (1) is 5-9 times of tricresyl phosphate (4- aminophenyl) ester and Zifrosilone quality sum.
8. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
The molar ratio for stating the DOPO in step (2) and the Zifrosilone in step (1) is 1:1.
9. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that: institute
Stating the reaction temperature in step (2) is 75 DEG C.
10. a kind of preparation method of siliceous and fluorine DOPO derivative flame retardant as claimed in claim 2, it is characterised in that:
Reaction time in the step (2) is 5-9 h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710119891.6A CN106831878B (en) | 2017-03-02 | 2017-03-02 | A kind of siliceous and fluorine DOPO derivative flame retardant and preparation method thereof |
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|---|---|---|---|
| CN201710119891.6A CN106831878B (en) | 2017-03-02 | 2017-03-02 | A kind of siliceous and fluorine DOPO derivative flame retardant and preparation method thereof |
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| CN106831878A CN106831878A (en) | 2017-06-13 |
| CN106831878B true CN106831878B (en) | 2019-04-09 |
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| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
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| US8227138B2 (en) * | 2007-11-02 | 2012-07-24 | Samsung Electronics Co., Ltd. | Phosphorus containing benzoxazine-based monomer, polymer thereof, electrode for fuel cell including the polymer, electrolyte membrane for fuel cell including the polymer, and fuel cell using the electrode |
| JP5417770B2 (en) * | 2008-08-27 | 2014-02-19 | 東洋インキＳｃホールディングス株式会社 | Flame retardant and flame retardant resin composition |
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| CN105732715A (en) * | 2016-01-27 | 2016-07-06 | 厦门大学 | Phosphorus-containing fluorine-containing synergic flame-retardant compound and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Wenchao Zhang等.Mechanical and thermal properties and flame retardancy of phosphorus-containing polyhedral oligomeric silsesquioxane (DOPO-POSS)/polycarbonate composites.《Polymer Degradation and Stability》.2010,第95卷第2541-2546页. |
| 有机磷阻燃剂的合成及在阻燃高分子材料中的应用研究进展;石延超 等;《高分子材料科学与工程》;20160531;第32卷(第5期);第167-175页 |
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